DE112018005944B4 - Elastic polyurethane fiber and its winding body - Google Patents

Abstract

An elastic polyurethane fiber in the form of a multifilament yarn, wherein the elastic polyurethane fiber comprises an ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B in a content of 50 ppm to 5% based on the weight of the elastic polyurethane fiber, wherein Compound A is selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms, tricarboxylic acids with 4 to 30 carbon atoms and phosphoric acid and compound B from monools with 1 to 30 carbon atoms, diols with a molecular weight of 3000 g / mol or less and Triols having a molecular weight of 3000 g/mol or less are selected, and wherein the ratio of the maximum to the minimum diameter of monofilaments constituting the multifilament yarn made of elastic polyurethane fibers is 1.1 to 2.0.

Description

Area

The present invention relates to an elastic polyurethane fiber and its winding body.

background

Elastic polyurethane fibers have excellent elastic properties and are therefore used in a variety of products that require stretch and fit, such as underwear, stockings, compression garments and diapers. As the processing speed of elastic polyurethane fibers in the manufacture of such products continues to increase year after year, there is a strong need for elastic polyurethane fibers and their packages that do not tear during processing.

Elastic polyurethane fibers also have a fineness suitable for various purposes, and depending on their size, they are often produced as multifilament yarns in bundles of several filaments.

However, when elastic polyurethane fibers are processed as multifilament yarn, the monofilaments may unravel during running, fluctuating tension may cause the yarn to become entangled with the guide, problems such as heat breaking of the monofilaments occur in steps where heat is applied, such as a dyeing step or a heat-setting step during the processing of a textile or a step of coating with a hot glue during the production of diapers, and these are all causes of yarn breakage.

Numerous modified techniques have been proposed to solve the problem of yarn breaking during processing, but it is still difficult to produce elastic polyurethane fibers that are resistant to monofilament separation, have a small variation in running tension, and are resistant to breaking Monofilaments are affected by heat and therefore their effects in preventing yarn breakage cannot be considered sufficient.

For example, with the elastic polyurethane fiber described in PTL 1, it is possible to make monofilaments resistant to unraveling by adjusting the false twist strength to cause cohesion of the monofilaments, but this leads to a high variation in running tension and an insufficient inhibiting effect against tearing of the yarn.

With the elastic polyurethane fiber described in PTL 2, it is possible to make monofilaments resistant to separation by low-molecularization of a part of the polyurethane polymer, but since the melting point of the polymer is also lowered, the heat resistance is less than satisfactory and the problem of breaking yarns often occurs on when processed hot.

PTL 3 discloses a processing agent for processing urethane elastomer fibers containing a dispersion medium of a certain kind having mineral oil as a main component and a dispersoid of a certain kind including an aliphatic ester compound. The disperse medium is 80-99.99% by mass and the dispersoid is 0.01-20% by mass, so a total of 100% by mass. The average particle size of the dispersoid is prepared to be in the range of 0.01-500 µm as measured by a specific measurement method.

PTL 4 discloses an elastic polyurethane yarn prepared using a polymer diol and a diisocyanate as starting materials. The elastic polyurethane yarn is provided by the incorporation of an aromatic condensed phosphate ester. The aromatic fused phosphate ester is 1,3-phenylenebis(dixylenyl phosphate) and the elastic polyurethane yarn has self-extinguishing property according to the FMVSS-302 method of the Federal Motor Vehicle Safety Standard.

List of literary citations

Patent literature

• [PTL 1] Japanese Examined Patent Document SHO JP S47 - 50 005 B1
• [PTL 2] Japanese Patent Disclosure JP 2006- 118 102 A
• [PTL 3] US 2011/0 046 317 A1
• [PTL 4] JP 2010 - 121 240 A

Short description

Technical problem

In light of these problems of the prior art, it is an object of the present invention to provide an elastic polyurethane fiber and its package, wherein the monofilaments are resistant to separation, the variation in running tension is small and the monofilaments are tear-resistant even when heated, so that tearing of the yarn can be sufficiently inhibited during processing.

the solution of the problem

As a result of many careful experiments aimed at solving the problem described above, the inventors completed this invention after unexpectedly finding that the problem can be solved by adding an ester or phosphoric acid ester in a predetermined amount to an elastic polyurethane fiber .

In particular, the present invention provides:

[1] Elastic polyurethane fiber in the form of a multifilament yarn, wherein the elastic polyurethane fiber comprises an ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B in a content of 50 ppm to 5% based on the weight of the elastic Polyurethane fiber, wherein compound A is selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms, tricarboxylic acids with 4 to 30 carbon atoms and phosphoric acid and compound B from monools with 1 to 30 carbon atoms, diols with a molecular weight of 3000 g / mol or less and triplets having a molecular weight of 3000 g/mol or less, and wherein the ratio of the maximum to minimum diameter of monofilaments constituting the multifilament yarn of elastic polyurethane fibers is 1.1 to 2.0.

[2] Elastic polyurethane fiber according to the above item [1], wherein the starting flow temperature of the elastic polyurethane fiber measured with a flow tester is 200 ° C or more.

[3] An elastic polyurethane fiber according to any one of [1] or [2] above, wherein the content of ester or phosphoric acid ester is 50 ppm or more and 1.5% or less based on the weight of the elastic polyurethane fiber.

[4] An elastic polyurethane fiber according to any one of [1] to [3] above, wherein compound A is selected from monocarboxylic acids having 4 to 30 carbon atoms, dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms.

[5] Elastic polyurethane fiber according to any one of the above [1] to [4], wherein compound A is selected from dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms, or compound B is selected from diols having a molecular weight of 3000 g/mol or less and triols having a molecular weight of 3000 g/mol or less.

[6] An elastic polyurethane fiber according to any one of [1] to [5] above, wherein the ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B has an aromatic ring.

[7] An elastic polyurethane fiber according to any one of [1] to [6] above, further comprising a tertiary amine-containing urethane or urea compound in a proportion of 0.01% or more and 5% or less.

wobei R₁ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist, R₂ und R₃ jeweils unabhängig eine zweiwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen sind und R₄ eine einwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen ist.[8] An elastic polyurethane fiber according to [7] above, wherein the tertiary amine-containing urethane compound is a urethane compound having a repeating unit represented by the following formula (1):

where R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, R ₂ and R ₃ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

• eine Repetiereinheit, welche durch die folgende Formel (1) wiedergegeben wird:
  
  wobei R₁ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist, R₂ und R₃ jeweils unabhängig eine zweiwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen sind und R₄ eine einwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen ist; und
• eine Repetiereinheit, welche durch Formel (2) wiedergegeben wird:
  
  wobei R₅ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist und R₆ eine zweiwertige Kohlenwasserstoffgruppe oder Polyoxyalkylengruppe mit 1 bis 10 Kohlenstoffatomen ist.

[9] An elastic polyurethane fiber according to [7] above, wherein the tertiary amine-containing urethane compound is a urethane compound comprising:

• a repeating unit, which is represented by the following formula (1):
  
  wherein R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, R ₂ and R ₃ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms; and
• a repeating unit, which is represented by formula (2):
  
  where R ₅ is a divalent hydrocarbon group having 5 to 30 carbon atoms and R ₆ is a divalent hydrocarbon group or polyoxyalkylene group having 1 to 10 carbon atoms.

wobei R₇ und R₈ jeweils unabhängig eine einwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen sind und R₉ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist.[10] Elastic polyurethane fiber according to the above item [7], wherein the tertiary amine-containing urea compound is a urea compound represented by the following formula (3):

where R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and R ₉ is a divalent hydrocarbon group having 5 to 30 carbon atoms.

[11] Elastic polyurethane fiber according to any one of [7] to [10] above, wherein the content of the urethane or urea compound containing a tertiary amine is greater than the content of the ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B.

[12] Elastic polyurethane fiber according to the above item [11], wherein the content of the tertiary amine-containing urethane or urea compound is 20 times to 150 times the content of the ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B is.

[13] Bobbin of an elastic polyurethane fiber according to one of the above points [1] to [12].

[14] The bobbin according to the above item [13], wherein the percentage elongation of the elastic polyurethane fiber on the bobbin is 5% or less.

Advantageous effects of the invention

By adding a specific ester or phosphoric acid ester in a predetermined amount to the elastic polyurethane fiber of the invention, it is possible that the elastic polyurethane fiber becomes resistant to monofilament separation, has a small variation in running tension and is resistant to breakage of the monofilaments by heat, whereby the tearing of the yarns during processing is sufficiently inhibited.

Brief description of the drawings

• 1 is a schematic diagram of an apparatus for measuring the variation in running tension of an elastic polyurethane fiber.
• 2 is a schematic diagram of an apparatus for measuring the antistatic property of an elastic polyurethane fiber while it is running.

Description of embodiments

An embodiment for carrying out the invention (hereinafter referred to as “this embodiment”) will now be described in detail. However, the invention is not limited to the embodiment described below, and various modifications may be made within its scope.

The polyurethane elastic fiber of this embodiment is a multifilament yarn composed of a plurality of monofilaments, the polyurethane elastic fiber comprising an ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B in a content of 50 ppm to 5% , based on the weight of the elastic polyurethane fiber, where compound A is selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms, tricarboxylic acids with 4 to 30 carbon atoms and phosphoric acid and compound B from monools with 1 to 30 carbon atoms, diols with a molecular weight of 3000 g/mol or less and triols having a molecular weight of 3000 g/mol or less.

For this embodiment, the polyurethane constituting the polyurethane elastic fiber is not particularly limited as long as it has a structure polymerized from, for example, a diisocyanate, polymer polyol, diol or diamine. The polymerization process is also not particularly limited. The polyurethane may, for example, be a polyurethane polymerized from a diisocyanate, polymer polyol and low molecular weight diamine as a chain extender (also known as "polyurethaneurea"), or a polyurethane polymerized from a diisocyanate, polymer polyol and low molecular weight diol as a chain extender (also known as as “polyurethane urethane”). A tri- or higher functional glycol or isocyanate can also be used in a range that does not affect the desired effect.

Diisocyanates include aromatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates. The aromatic diisocyanates include, among others, diphenylmethane diisocyanate (hereinafter also referred to as “MDI”), tolylene diisocyanate, 1,4-diisocyanatobenzene, xylylene diisocyanate and 2,6-naphthalene diisocyanate. Examples of alicyclic diisocyanates and aliphatic diisocyanates are methylenebis(cyclohexyl isocyanate) (hereinafter also referred to as “H12MDI”), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate , hexahydrotolylene diisocyanate and octahydro-1,5-naphthalene diisocyanate. These diisocyanates can be used alone, or two or more can be used in combination. Particularly from the viewpoint of the stretch recovery ability of elastic filaments, the diisocyanate is preferably an aromatic diisocyanate and particularly preferably MDI.

The polymer polyols include, among others, polymer diols such as polyether-based diols, polyester-based diols, polycarbonate-based diols, polyacrylic-based diols, polythioester-based diols and polyhydrocarbon-based diols. From the viewpoint of hydrolysis resistance, the polymer polyol is preferably a polyether-based polyol, and particularly preferably a polyether-based diol.

Examples of polyether-based polyols are polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter also referred to as "PTMG"), modified PTMG, as a copolymer of tetrahydrofuran (THF) and neopentyl glycol (hereinafter also referred to as "PTXG") , and diols, which are copolymers of THF and 3-methyl-THF. Any of these polyether-based polyols may be used alone, or two or more may be used in combination. The number average molecular weight of the polymer diol is preferably 1,000 to 8,000. By using a polymer diol in this range, it is possible to easily obtain an elastic fiber excellent in elongation, elongation recovery ability and heat resistance. From the viewpoint of UV brittleness, the polyether-based polyol is preferably PTMG, PTXG or a polyol that is a mixture of these.

The chain extender is preferably one or more selected from the group consisting of low molecular weight diamines and low molecular weight diols. A chain extender can also be one that has both a hydroxy group and an amino group in the molecule, such as ethanolamine.

Low molecular weight diamines as chain extenders are not particularly limited, and examples thereof include hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,2-diaminobutane, 1,3-diaminobutane , 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,2-dimethylbutane, 2,4-diamino-1-methylcyclohexane , 1,3-pentanediamine, 1,3-cyclohexanediamine, bis(4-aminophenyl)phosphine oxide, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine and bis(4-aminophenyl)phosphine oxide. These low molecular weight diamines can be used alone, or two or more can be used in combination. From the viewpoint of the stretch recovery ability of the elastic filament, the low molecular weight diamine is preferably a diamine having 2 to 5 carbon atoms, and particularly preferably ethylenediamine.

The low molecular weight diol may include, but is not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, and 1-methyl-1,2-ethanediol. These low molecular weight diols can be used alone, or two or more can be used in combination.

There are no particular limitations on the polymerization process for polyurethanes polymerized from such diisocyanates, polymer polyols, diols and diamines, and it may be melt polymerization or solution polymerization. In the case of solution polymerization, a polyurethane solution can be obtained by polymerization using diisocyanate, polymer polyol, diol and diamine starting materials in a solvent such as DMAc, DMF, DMSO or NMP. The reaction process for the polymerization of a polyurethane is not particularly limited, and it may be a one-shot process in which the starting materials are introduced into a solvent and reacted at a suitable temperature, or a prepolymer process in which the diisocyanate and the polymer polyol is reacted with each other to form a prepolymer, followed by a chain extension reaction with the diol or diamine to synthesize the polyurethane.

As long as the desired effect is not hindered, the polyurethane elastic fiber may also include a commonly known organic or inorganic compound used in polyurethane elastic fibers, such as a polymer other than polyurethane, or an antioxidant, a heat stabilizer, an antistatic agent, a light fastness agent, a UV -Absorber, a gas discoloration inhibitor, a dye, an activator, a matting agent, a colorant, a filler, an anti-adhesive agent or a lubricant.

The spinning process for the elastic polyurethane fiber is not particularly limited. Examples of the spinning process include processes for dissolving polyurethane in a solvent and spinning it by a wet process or dry process, and processes for hot-melting polyurethane and spinning it by a melt process.

The polyurethane elastic fiber of this embodiment may have a polyurethane elastic fiber lubricant externally adhered during spinning by a conventional, well-known method. The method of adhering a lubricant may be, for example, a method using an oil roller. The lubricant component to be used may be, among others, combinations of different substances, including waxes that are solids at ordinary temperatures, examples of which are silicone-based oils such as dimethyl silicone, polyether-modified silicone or polyamino-modified silicone, mineral oil-based oils, fine mineral particles , such as talc, silicon oxide or colloidal clay, powders of metal salts of higher fatty acids such as magnesium stearate or calcium stearate, carboxylic acids in the form of higher fatty acids, higher aliphatic alcohols and paraffinic polyethylene.

For this embodiment, adding the ester or phosphoric acid ester to the polyurethane elastic fiber in an amount of 50 ppm to 5% based on the weight of the polyurethane elastic fiber has an effect of making the fiber resistant to monofilament separation with little variation the running tension and to be resistant to tearing of the monofilaments under heat, whereby the tearing of the yarn during processing is sufficiently inhibited.

• einer, die aus Monocarbonsäuren mit 4 bis 30 Kohlenstoffatomen, Dicarbonsäuren mit 4 bis 30 Kohlenstoffatomen, Tricarbonsäuren mit 4 bis 30 Kohlenstoffatomen und Phosphorsäure ausgewählt ist, und Verbindung B:
• einer, die aus Monoolen mit 1 bis 30 Kohlenstoffatomen, Diolen mit einem Molekulargewicht von 3000 g/mol oder weniger und Triolen mit einem Molekulargewicht von 3000 g/mol oder weniger ausgewählt ist.

As mentioned above, the ester or phosphoric ester added to the polyurethane elastic fiber of this embodiment is the product of condensation of Compound A:

• one selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms, tricarboxylic acids with 4 to 30 carbon atoms and phosphoric acid, and compound B:
• one selected from monools having 1 to 30 carbon atoms, diols having a molecular weight of 3000 g/mol or less, and triols having a molecular weight of 3000 g/mol or less.

It is sufficient if the ester or phosphoric acid ester is added to the elastic polyurethane fiber in the predetermined amount, without subjecting any particular limitation to the form of "addition" which is addition to the polyurethane polymer or adhesion to the fiber surface together with a treatment agent, such as a lubricant. The method of addition to the polyurethane polymer is not particularly limited, and any of various means such as a method using a static mixer, a stirring method, a method using a homomixer, or a method using a twin-screw extruder can be employed. The method of using a treating agent such as a lubricant is also not particularly limited, and any of various means can be used, such as a method of adding an ester or phosphoric ester to a lubricant in advance and using an oil roller or spray nozzle , to make it adhere to the elastic polyurethane fiber together with the lubricant.

The reason why the monofilament can be made resistant to separation by adding the ester or phosphoric ester to the polyurethane elastic fiber is not entirely clear, but the inventors draw the following conclusions. Since the ester or phosphoric acid ester has poor compatibility with the polyurethane polymer regardless of the method of addition to the polyurethane elastic fiber, it bleeds easily from the elastic fiber and tends to localize on the surfaces of the monofilaments. The ester or phosphoric acid ester that localizes on the surface is believed to be resistant to monofilament separation due to mutual attraction through intermolecular forces between similar structures, such as ester groups.

For this embodiment, compound A as a starting material before the condensation reaction of the ester or phosphoric ester is one selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms, tricarboxylic acids with 4 to 30 carbon atoms and phosphoric acid. When compound A is a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, a tricarboxylic acid having 4 to 30 carbon atoms or phosphoric acid, it is possible to inhibit the separation of the monofilaments. There are no particular restrictions on the branching or substituents of the monocarboxylic acid, dicarboxylic acid or tricarboxylic acid. The term "optionally substituted" means that compound A may have any other bonds or optional substituents as long as it has a monocarboxylic acid, dicarboxylic acid or tricarboxylic acid structure, and for example it may have a bond such as an ester bond, amide bond, ether bond, sulfide bond, disulfide bond or urethane bond, or a group such as an epoxide, nitro, cyano, ketone, formyl, acetal, thioacetal or sulfonyl group. The monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms and tricarboxylic acids with 4 to 30 carbon atoms can be, for example, benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, citric acid, lauric acid, myristic acid, Stearic acid, oleic acid or epoxidized vegetable oils.

For this embodiment, compound B as a starting material before the condensation reaction of the ester or phosphoric ester is one selected from monools having 1 to 30 carbon atoms, diols having a molecular weight of 3000 g/mol or less, and triols having a molecular weight of 3000 g/mol or less is. When compound B is a monool having 30 or fewer carbon atoms, a diol having a molecular weight of 3,000 g/mol or less, or a triol having a molecular weight of 3,000 g/mol or less, it is possible to inhibit the separation of the monofilaments. There are no special restrictions on branching or substituents. The term "optionally substituted" means that compound B may have any other bonds or optional substituents as long as it has a monool, diol or triol, and for example it may have a bond such as an ester bond, amide bond, ether bond, sulfide bond, disulfide bond or Urethane bond, or a group such as an epoxide, nitro, cyano, ketone, formyl, acetal, thioacetal or sulfonyl group. Examples of compound B are monools such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexyl alcohol, 2-ethyl-1-hexanol, 1-nonanol, isodecyl alcohol, phenol and benzyl alcohol, diols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 ,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol, and triols such as glycerin and 1,2,4-butanetriol.

From the viewpoint of effectively inhibiting the separation of monofilaments for this embodiment, compound B is preferably a monool having 15 or fewer carbon atoms, a diol having a molecular weight of 1500 g/mol or less, or a triol having a molecular weight of 1500 g/mol or less , particularly preferably a monool with 15 or fewer carbon atoms, a diol with a molecular weight of 500 g / mol or less or a triol with a molecular weight of 500 g / mol or less, most preferably a monool with 15 or fewer carbon atoms or a diol having a molecular weight of 500 g/mol or less, and most preferably a diol having a molecular weight of 500 g/mol or less. Diols having a molecular weight of 500 g/mol or less include ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol. An ester or phosphoric acid ester comprising compound B bleeds more easily from the elastic fiber and localizes more easily on the surface of the monofilaments.

From the viewpoint of effectively inhibiting the variation of the running tension for this embodiment, compound A is preferably one selected from monocarboxylic acids having 4 to 30 carbon atoms, dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms. The reason that the variation in running tension is more effectively inhibited when Compound A is one selected from monocarboxylic acids having 4 to 30 carbon atoms, dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms is not entirely clear, however the inventors draw the following conclusions. When compound A is one selected from monocarboxylic acids having 4 to 30 carbon atoms, dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms as described above, the surface tackiness of the filament is lower and it is possible to Degree and the variation of frictional resistance between the filament and the guide and rollers that form the travel path of the filament, which makes it possible to reduce the variation in tension of the running filament.

From the viewpoint of effectively inhibiting the separation of the monofilaments for this embodiment, compound A is preferably one selected from dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms, or compound B is one selected from diols having a molecular weight of 3000 g/mol or less and triols with a molecular weight of 3000 g/mol or less are selected. While it is not entirely clear why the separation of monofilaments can be inhibited more effectively when compound A is one selected from dicarboxylic acids with 4 to 30 carbon atoms and tricarboxylic acids with 4 to 30 carbon atoms, or compound B is one selected from diols with a molecular weight of 3000 g/mol or less and triols with a molecular weight of 3000 g/mol or less, i.e. when the ester is polyvalent, the inventors draw the following conclusions. When compound A is one selected from dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms, or compound B is one selected from diols having a molecular weight of 3000 g/mol or less and triols having a molecular weight of 3000 g/mol or less, the condensed compound of Compound A and Compound B bleeds out of the elastic fiber more easily and tends to localize on the surfaces of the monofilaments, which further strengthens the mutual attraction between the monofilaments and makes the monofilaments durable towards the separation.

From the viewpoint of more effectively inhibiting the separation of the monofilaments for this embodiment, compound A is preferably a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, or a tricarboxylic acid having 4 to 30 carbon atoms comprising an aromatic ring, and is most preferably a monocarboxylic acid with 4 to 15 carbon atoms, a dicarboxylic acid with 4 to 15 carbon atoms or a tricarboxylic acid with 4 to 15 carbon atoms comprising an aromatic ring, and especially benzoic acid, phthalic acid, terephthalic acid or trimellitic acid. The reason why the separation of monofilaments can be inhibited more effectively when Compound A has an aromatic ring is not entirely clear, but the inventors draw the following conclusions. When compound A has an aromatic ring, as mentioned above, intermolecular forces between the aromatic rings presumably act to further strengthen the mutual attraction between the monofilaments, making the monofilaments more resistant to separation.

The content of the ester or phosphoric acid ester, based on the weight of the elastic polyurethane fiber, for this embodiment is 50 ppm to 5%, particularly preferably 50 ppm to 2%, very particularly preferably 100 ppm to 2%, very particularly preferably 100 ppm to 1, 5% and most preferably 100 ppm to 1%. The “content” for this embodiment is the weight percentage based on the total weight of the elastic polyurethane fiber. When the ester or phosphoric acid ester is added by multiple methods, such as both within the polyurethane polymer and added in a treating agent such as a lubricant, the "content" refers to their total value. Various types of esters or phosphoric esters can also be added to the polyurethane elastic fiber at the same time. If the content of the ester or phosphoric ester is 5% or less, it may inhibit the effect of the ester or phosphoric ester in plasticizing the polymer and may reduce the variation in running tension. The inhibiting effect on the variation of tensile force becomes more effective by limiting the content to 2% or less, it becomes more effective by limiting it to 1.5% or less, and it becomes most effective by limiting it to 1% or less limited. A content of the ester or phosphoric acid ester of 50 ppm or more provides an effect of inhibiting the separation of the monofilaments. This effect is more effective when the content is 100 ppm or more.

For this embodiment, the ester or phosphoric acid ester added to the elastic polyurethane fiber preferably has a melting point of 60°C or below. A melting point of 60 °C or below can inhibit the separation of monofilaments more effectively. When the melting point of the ester or phosphoric ester is 60°C or below, the ester or phosphoric ester bleeds more easily from the elastic fiber and localizes more easily on the surfaces of the monofilaments.

For this embodiment, the boiling point of the ester or phosphoric ester added to the polyurethane elastic fiber is 100°C or higher at an air pressure of 1.013 × 10 ⁵ Pa. If the boiling point of the ester or phosphoric ester is 100°C or higher at an air pressure of 1.013 × 10 ⁵ Pa, the ester or phosphoric ester is unlikely to volatilize and it accumulates more easily in the elastic polyurethane fiber, which makes it possible to inhibit the separation of monofilaments more effectively.

The ester or phosphoric acid ester to be added to the polyurethane elastic fiber for this embodiment has a molecular weight of preferably 5,000 g/mol or less, more preferably 2,000 g/mol or less, and particularly from the viewpoint of effectively inhibiting the separation of the monofilaments preferably 1000 g/mol or less. If the molecular weight of the ester or phosphoric ester is low, the ester or phosphoric ester has increased fluidity and bleeds more easily from the monofilaments.

For this embodiment, the ester or phosphoric ester to be added to the elastic polyurethane fiber preferably has an oxygen atom adjacent to the ester group. By having an oxygen atom next to the ester group, it is possible to inhibit the separation of the monofilaments more effectively. If the ester or phosphoric ester has an oxygen atom adjacent to the ester group, intermolecular forces between the oxygen atoms different from those of the ester group in the ester or phosphoric ester act to further strengthen the mutual attraction between the monofilaments, making it less likely that the monofilaments separate.

For this embodiment, the ester or phosphoric ester need only be a condensation product of Compound A and Compound B, but from the viewpoint of more effectively inhibiting the separation of the monofilaments, the ester or phosphoric ester preferably has an aromatic ring. Examples of esters or phosphoric acid esters without aromatic rings are bis(2-cyclohexyl) adipate, trimethyl citrate, bis(2-ethylhexyl) adipate, bisoctyl adipate, dibutyl sebacate and dioctyl sebacate. Examples of esters or phosphoric acid esters with aromatic rings are benzoic acid esters, such as methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, (2-ethylhexyl) benzoate, phenyl benzoate, benzyl benzoate, ethylene glycol benzoate, propylene glycol benzoate, diethylene glycol benzoate, dipropylene glycol benzoate, ethylene glycol ibenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate and 1 ,4-Cyclohexanedimethanol dibenzoate, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate and bisbutyl benzyl phthalate, terephthalic acid esters such as dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate , diisobutyl terephthalate, dihexyl terephthalate, bis(2 -ethylhexyl) terephthalate, diisononyl terephthalate, dibenzyl terephthalate, dicyclohexyl terephthalate and butyl benzyl terephthalate, trimellitic acid esters such as trimethyl trimellitate, trioctyl trimellitate and tris (2-ethylhexyl) trimellitate, and aromatic phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate and diphenyl (2-ethylh exyl)phosphate. From the point of view of more effective inhibition of the separation of the monofilaments, the ester or phosphoric acid ester is particularly preferably a benzoic acid ester, such as methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, (2-ethylhexyl) benzoate, phenyl benzoate, benzyl benzoate, ethylene glycol benzoate, propylene glycol benzoate, diethylene glycol benzoate, Di propylene glycol benzoate, Ethylene glycol dibenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate or 1,4-cyclohexanedimethanol dibenzoate. From the standpoint of most effectively inhibiting the separation of the monofilaments, the ester or phosphoric acid ester is preferably a benzoic acid ester having a plurality of aromatic rings and is most preferably in particular ethylene glycol dibenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate or 1,4-cyclohexanedimethanol dibenzoate.

For this embodiment, the size of the polyurethane elastic fiber is preferably 100 dtex or larger. When the size is 100 dtex or larger, it is possible to inhibit the yarn breaking in heat more effectively.

For this embodiment, the number of filaments of the polyurethane elastic fiber as a multifilament yarn is preferably 20 or more. When the number of filaments is 20 or more, it is easier to obtain an elastic polyurethane fiber having good elongation property.

For this embodiment, the monofilament size of the polyurethane elastic fiber is preferably 30 dtex or lower. When the monofilament size is 30 dtex or lower, it is possible to effectively cause evaporation of the solvent when producing by a dry spinning method.

For a further increased effect on the separation of monofilaments for this embodiment, the ester or phosphoric acid ester is added in an amount of 50 ppm to 5%, based on the weight of the elastic polyurethane fiber, and the ratio of the maximum to the minimum diameter of the monofilaments, which Form multifilament is 1.1 to 2.0. The ratio of the maximum to minimum diameter of the monofilaments is particularly preferably 1.2 to 2.0 and very particularly preferably 1.2 to 1.9. When the ratio of the maximum to minimum diameter of the monofilaments is 2.0 or less, there is less unbalance of the tension of each monofilament, and it is possible to inhibit the variation of the running tension, which helps to reduce the breaking of the yarn. This effect is more effective when the ratio of the maximum to minimum diameter of the monofilaments is 1.9 or less. When the ratio of the maximum to minimum diameter of the monofilaments is 1.1 or more, the monofilaments are less likely to unravel, this effect being more effective when the ratio of the maximum to minimum diameter of the monofilaments is 1.2 or more . The reason why the separation of the monofilaments can be made unlikely when the ratio of the monofilament diameters is 1.1 or more is not entirely clear, but the inventors draw the following conclusions. In an elastic multifilament fiber, the monofilaments are usually twisted in incorrect twisting steps or taking-up steps during production, resulting in a complex entanglement between the monofilaments. If the ratio of the maximum to minimum diameter of the monofilaments is 1.1 or more, this entanglement between the monofilaments is believed to become even more complex, further increasing the effect of the ester or phosphoric ester and allowing the monofilaments to be more resistant to separation. The method for controlling the ratio of the maximum to minimum diameter of the monofilaments is not particularly limited, but a suitable method is to align yarns ejected from two spinnerets with different numbers of holes to form the elastic polyurethane fiber. Specifically, the polyurethane stock solution is extruded from two spinnerets with different numbers of holes of equal weights and the solvent is evaporated, producing two yarns of the same size but with different numbers of filaments, which are then aligned parallel in a false twisting step, where a single elastic polyurethane fiber is created. As a more specific example, the polyurethane stock solution can be extruded from spinnerets with 48 or 24 holes, respectively, each with a weight of 310 dtex of yarn, producing two yarns which are then aligned parallel in a false twisting step, in this case the elastic polyurethane fiber as a whole 620 dtex with 72 filaments, but since the monofilaments from the 24-hole spinneret have approximately 1.5 times the monofilament diameter of the monofilaments from the 48-hole spinneret, one can assume that the ratio of the maximum to the minimum diameter of the monofilaments is about 1.5. As another method for controlling the ratio of the maximum to the minimum diameter of the monofilaments, it is suitable to employ a method in which the temperature in the spinning cylinder is adjusted during spinning to appropriately cause rocking of the yarn, or a method in which the speed of a godet is adjusted during take-up in such a way that the tensile force of the elastic fiber in the spinning cylinder is controlled.

For this embodiment, the starting flow temperature of the elastic polyurethane fiber measured with a flow tester is preferably 200 ° C or more. When the flow initiation temperature is 200°C or more, it is possible to obtain sufficient heat resistance so that yarn breakage due to heat does not occur even if a high temperature is applied to the polyurethane elastic fiber during processing. The method for producing an elastic polyurethane fiber having a flow initiation temperature of 200° C. or more is not particularly limited, and may be, for example, a method in which the number average molecular weight of the polyurethane polymer is adjusted above a fixed weight in which the hard segment content in the polymer is increased, or a method in which a well-known heat resistance improver is added. The chain extender in the polyurethane elastic fiber may be any one selected from the group consisting of low molecular weight diamines and low molecular weight diols, but when using a low molecular weight diamine, the formation of a hard segment including a urea group is enabled, resulting in that a stronger hydrogen bonding force acts than a hard segment containing a urethane group, which is formed when using a low molecular weight diol, and which increases the flow initiation temperature and facilitates the flow initiation temperature to be 200 ° C or more.

From the viewpoint of more effectively inhibiting the separation of the monofilaments and more effectively increasing the antistatic property (ie, resistance to static electricity) during running for this embodiment, the tertiary amine-containing urethane or urine compound preferably added in a proportion of 0.01% or more and 5% or less, more preferably added in a proportion of 0.01% or more and 3% or less and most preferably added in a proportion of 0.03% or more and 3% or less added based on the weight of the elastic polyurethane fiber. The tertiary amine-containing urethane or urea compound may include a tertiary amine and a urethane or urea group in the molecule, without limitation to the position of the tertiary amine and the urethane or urea group in the molecule, which are at the ends or within the molecule instead of at the ends. When a tertiary amine and a urethane or urea group are contained in the molecule, there are no particular restrictions on their number and no particular restrictions on the presence of substituents in the molecule or its molecular weight. The reason why the monofilaments become more effectively resistant to separation by adding a tertiary amine-containing urethane or urea compound in a proportion of 0.01% or more and 5% or less is not entirely clear, but the inventors consider this following conclusions. By adding a tertiary amine-containing urethane or urea compound to the polyurethane elastic fiber, the effect of bleeding the ester or phosphoric ester from the elastic fiber is promoted, making it more likely that the ester or phosphoric ester are localized on the surfaces of the monofilaments, so that the force of mutual attraction between the monofilaments is further strengthened and the monofilaments are less likely to separate. This effect becomes more effective when the tertiary amine-containing urethane or urea compound is added in a proportion of 0.03% or more. From an economic perspective, the content of the tertiary amine-containing urethane or urea compound is preferably 5% or less. The reason why the antistatic property during running can be more effectively expressed by adding a tertiary amine-containing urethane or urea compound in a proportion of 0.01% or more and 5% or less is not entirely clear, but the Inventors draw the following conclusions. By adding a tertiary amine-containing urethane or urea compound to the polyurethane elastic fiber, the oxygen atoms and nitrogen atoms, which are the polar moieties of the urethane or urea compounds, and the ester groups of ester compounds may interact with each other, providing a path for electrons is created so that the polyurethane is less likely to become electrically charged. This effect becomes more effective when the tertiary amine-containing urethane or urea compound is added in a proportion of 0.03% or more.

wobei R₁ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist, R₂ und R₃ jeweils unabhängig eine zweiwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen sind und R₄ eine einwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen ist; oder
eine Urethanverbindung, die Folgendes aufweist:
eine Repetiereinheit, welche durch die folgende Formel (1) wiedergegeben wird:

wobei R₁ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist, R₂ und R₃ jeweils unabhängig eine zweiwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen sind und R₄ eine einwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen ist; und
eine Repetiereinheit, welche durch Formel (2) wiedergegeben wird:

wobei R₅ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist und R₆ eine zweiwertige Kohlenwasserstoffgruppe oder Polyoxyalkylengruppe mit 1 bis 10 Kohlenstoffatomen ist. Die ein tertiäres Amin enthaltende Harnstoffverbindung ist vorzugsweise eine Harnstoffverbindung, die durch die folgende Formel (3) wiedergegeben wird:

wobei R₇ und R₈ jeweils unabhängig eine einwertige Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen sind und R₉ eine zweiwertige Kohlenwasserstoffgruppe mit 5 bis 30 Kohlenstoffatomen ist.From the viewpoint of more effectively inhibiting the separation of the monofilaments and more effectively increasing the antistatic property during running for this embodiment, the tertiary amine-containing urethane compound is preferably a urethane compound having a repeating unit represented by the following formula (1):

wherein R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, R ₂ and R ₃ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms; or
a urethane compound comprising:
a repeating unit, which is represented by the following formula (1):

wherein R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, R ₂ and R ₃ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms; and
a repeating unit, which is represented by formula (2):

where R ₅ is a divalent hydrocarbon group having 5 to 30 carbon atoms and R ₆ is a divalent hydrocarbon group or polyoxyalkylene group having 1 to 10 carbon atoms. The tertiary amine-containing urea compound is preferably a urea compound represented by the following formula (3):

where R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and R ₉ is a divalent hydrocarbon group having 5 to 30 carbon atoms.

Particularly preferably, R ₁ and R ₅ are each independently a divalent hydrocarbon group having 5 to 15 carbon atoms, most preferably they have an alicyclic hydrocarbon structure, and most preferably they have an alicyclic hydrocarbon structure with a six-membered ring.

R ₂ and R ₃ are very particularly preferably hydrocarbon groups with 1 to 5 carbon atoms. Examples of hydrocarbon groups with 1 to 5 carbon atoms include methylene, ethylene, propylene, trimethylene, butylene, 2-methylpropylene and pentylene groups.

R ₄ is most preferably a hydrocarbon group with 1 to 5 carbon atoms. Examples of hydrocarbon groups with 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl and t-pentyl groups.

R ₆ is particularly preferably a divalent hydrocarbon group with 2 to 4 carbon atoms or an oxyethylene, oxypropylene, oxytetramethylene, polyoxyethylene, polyoxypropylene or polyoxytetramethylene group. There is no particular limitation on the molecular weight of an oxytetramethylene, polyoxyethylene, polyoxypropylene or polyoxytetramethylene group.

In the tertiary amine-containing urethane compound, there is no particular limitation on the number of repeating units represented by formula (1) and the number of repeating units represented by formula (2), and they may be repeating units represented by formula (1), and repeat units represented by formula (2) located at arbitrary positions in the molecule.

R ₇ and R ₈ are particularly preferably hydrocarbon groups with 1 to 5 carbon atoms. Examples of hydrocarbon groups with 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl and t-pentyl groups.

R ₉ is particularly preferably a hydrocarbon group with 5 to 15 carbon atoms and particularly preferably has an aromatic ring structure. Examples of structures with aromatic ring structures include benzene structures and diphenylmethane structures.

Specific examples of urethane compounds having a repeating unit represented by formula (1) include:

Compound 4 obtained by copolymerization of isophorone diisocyanate and N-butyldiethanolamine and having a repeating unit represented by the following formula (4):

und Verbindung 6, die durch Copolymerisation von Isophorondiisocyanat und 1,1'-{N-(t-Butyl)imino}di-2-propanol erhalten wird und eine Repetiereinheit aufweist, die durch die folgende Formel (6) dargestellt wird:

Compound 5 obtained by copolymerization of dicyclohexylmethane-4,4'-diisocyanate and 1,1'-(N-methylimino)di-2-propanol and having a repeat unit represented by the following formula (5):

and Compound 6, which is obtained by copolymerization of isophorone diisocyanate and 1,1'-{N-(t-butyl)imino}di-2-propanol and has a repeat unit represented by the following formula (6):

und eine Repetiereinheit aufweist, die durch die folgende Formel (8) dargestellt wird:

Specific examples of urethane compounds having a repeating unit represented by formula (1) and a repeating unit represented by formula (2) include compound 7 obtained by copolymerization of dicyclohexylmethane-4,4'-diisocyanate, N -(t-Butyl)diethanolamine and 1,4-butanediol and has a repeating unit represented by the following formula (7):

and a repeating unit represented by the following formula (8):

und Verbindung 9, die durch die folgende Formel (10) dargestellt wird:

Specific examples of compounds represented by formula (3) are not particularly limited and include compound 8 represented by the following formula (9):

and compound 9, which is represented by the following formula (10):

For this embodiment, from the viewpoint of more effectively inhibiting the separation of the monofilaments and more effectively improving the antistatic property during running, the content of the tertiary amine-containing urethane or urea compound is preferably larger than the content of the ester or phosphoric acid ester, and the content of the urethane or urea compound containing a tertiary amine is particularly preferably 5 times to 200 times, very particularly preferably 10 times to 150 times, very particularly preferably 20 times to 150 times and most preferably 30 times to 150 times as large as the content of the ester or phosphoric acid ester.

For this embodiment, the percentage elongation of the elastic polyurethane fiber on the bobbin is preferably 5% or less. An elastic polyurethane fiber is usually wound onto a paper tube with a greater degree of elongation than in the relaxed state, forming a wound body. In the state of the winding body, the percentage elongation on the winding body is the proportion with which the elastic polyurethane fiber is stretched, based on the relaxed state. When this percentage elongation is 5% or less, this reduces the variation in tension required when the elastic fiber is unwound from the package, making it possible to more effectively inhibit the variation in tensile force during running. The method of reducing the percentage elongation to 5% or less is not particularly limited, and an example thereof is a method of adjusting the speed ratio between the godet and the winding spool when winding the polyurethane elastic fiber.

Since the polyurethane elastic fiber of this embodiment is resistant to separation of the monofilaments, has a small variation in running tension and has excellent antistatic properties during running, it is resistant to yarn breakage when combined with natural fibers such as cotton, silk or wool. polyamide fibers such as nylon 6 or nylon 66, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate or polytetramethylene terephthalate, cationically dyed polyester fibers, cuprammonium regenerated rayon, viscose rayon and acetate rayon, or when coated, blended or twisted with such fibers to produce finished yarn, and then woven to obtain textile fabrics, and therefore high productivity can be achieved.

A fabric using the polyurethane elastic fiber of this embodiment can be suitably used for purposes including swimwear, belts, bras, intimate apparel, various stretch bases such as underwear, tights, pantyhose, waistbands, bodysuits, leggings, stretch Sportswear, stretch streetwear, medical clothing and stretch clothing can be used. Since with a fabric using the polyurethane elastic fiber of this embodiment, the monofilaments of the polyurethane elastic fiber in the fabric are resistant to heat tearing even after thermal treatment steps such as presetting, dyeing and final setting and can prevent production of defective products it possible to achieve high productivity.

Since the elastic polyurethane fiber of this embodiment is resistant to separation of monofilaments, has a small variation in running tension, has excellent antistatic properties during running, is resistant to breakage of monofilaments even in heat and can sufficiently inhibit breakage of yarns, it enables Producing sanitary goods, such as sanitary products and paper diapers, with high productivity, while also having low breakage of yarns within elements and low loss of yarns, inhibiting the generation of defects in their products.

Examples

The present invention will now be explained in more detail with reference to the following examples and comparative examples, but the scope of the invention should not be construed as being limited by the examples.

The evaluation methods used in the examples are now explained.

Measurement procedures and evaluation procedures

Content of ester or phosphoric acid ester as a product of the condensation between compound A and compound B

An example of a method for detecting the ester or phosphoric ester is to use a well-known analytical method such as GC/MS or NMR after immersing a predetermined amount of the polyurethane elastic fiber in a solvent to extract the ester or phosphoric ester. As a more specific example, 1 g of elastic polyurethane fiber is subjected to Soxhlet extraction with 120 ml of chloroform for 8 hours. The extract is concentrated and dried at 40 °C with an evaporator and vacuum dried for 1 hour at ordinary temperature to obtain a dry sample, which is then analyzed by a well-known method such as GC/MS or NMR. In particular, for example, the following apparatus and conditions can be selected as analysis conditions.

NMR measurement

• Messapparatur: ECS400 von der JEOL Corp.
• Gemessener Atomkern: ¹H
• Resonanzfrequenz: 400 MHz
• Anzahl der Scans: 256
• Messtemperatur: Raumtemperatur
• Lösungsmittel: schweres Dimethylformamidhydrid
• Messkonzentration: 1,5 Gew.-%
• Referenz für chemische Verschiebung: Dimethylformamid (8,0233 ppm)

A predetermined amount of dry sample and dimethyl sulfoxide as an internal standard were weighed and measured by NMR under the following conditions, and the structure of the ester or phosphoric ester was determined and its content was calculated. The ester or phosphoric ester content can be calculated from the integral value of the hydrogen signal using dimethyl sulfoxide as an internal standard. For example, when calculating the content of diethylene glycol benzoate, it can be calculated by comparing the integral value for the hydrogen atoms of the phenyl group of diethylene glycol benzoate with the integral value for the hydrogen atoms of the methyl group of dimethyl sulfoxide. When it was not possible to measure the content due to overlap of signals in NMR, the content was measured by the GC/MS analysis described below.

• Measuring apparatus: ECS400 from JEOL Corp.
• Measured atomic nucleus: ¹ H
• Resonance frequency: 400 MHz
• Number of scans: 256
• Measuring temperature: room temperature
• Solvent: heavy dimethylformamide hydride
• Measuring concentration: 1.5% by weight
• Chemical Shift Reference: Dimethylformamide (8.0233 ppm)

GC/MS analysis

• GC-Apparatur: Agilent Technologies 7890A
• Einlasstemperatur: 320 °C
• Säule: DB-1 MS (30 m × 0,25 mm φ), Dicke der flüssigen Phase: 0,25 µm Säulentemperatur: 40 °C (Haltezeit: 5 Minuten), Temperaturerhöhung:
  • 20 °C/min, 320 °C (11 Minuten halten)
• MS-Apparatur: Agilent Technologies 5975C MSD
• Ionenquellentemperatur: 230 °C
• Ionisierungsverfahren: Elektronenionisierung

The dry sample is dissolved in 5 ml of methanol and analyzed. The concentration of the ester or phosphoric acid ester can be calculated as a weight percent by preparing a separate calibration curve for the ester or phosphoric acid ester whose structure was identified by NMR measurement using GC and comparing this with the area of the ester or phosphoric acid ester in compared to the dry sample.

• GC apparatus: Agilent Technologies 7890A
• Inlet temperature: 320°C
• Column: DB-1 MS (30 m × 0.25 mm φ), liquid phase thickness: 0.25 µm Column temperature: 40 °C (holding time: 5 minutes), temperature increase:
  • 20°C/min, 320°C (hold for 11 minutes)
• MS apparatus: Agilent Technologies 5975C MSD
• Ion source temperature: 230°C
• Ionization process: electron ionization

Content of tertiary amine containing urethane or urea compound

The method for detecting the urethane or urea compound may be, for example, a method in which a predetermined amount of the polyurethane elastic fiber is immersed in a solvent and the urethane or urea compound is extracted, and then a generally known analysis method such as GC/MS or NMR, applied. As a more specific example, 1 g of elastic polyurethane fiber is subjected to Soxhlet extraction with 120 ml of chloroform for 8 hours. The extract is concentrated and dried at 40 °C with an evaporator and vacuum dried for 1 hour at ordinary temperature to obtain a dry sample, which is then analyzed by a well-known method such as GC/MS or NMR. In particular, for example, the following apparatus and conditions can be selected as analysis conditions.

NMR measurement

• Messapparatur: ECS400 von der JEOL Corp.
• Gemessener Atomkern: ¹H
• Resonanzfrequenz: 400 MHz
• Anzahl der Scans: 256
• Messtemperatur: Raumtemperatur
• Lösungsmittel: schweres Dimethylformamidhydrid
• Messkonzentration: 1,5 Gew.-%
• Referenz für chemische Verschiebung: Dimethylformamid (8,0233 ppm)

A predetermined amount of dry sample and dimethyl sulfoxide as an internal standard were weighed and measured by NMR under the following conditions, and the structure of the urethane or urea compound was determined and the content thereof was calculated. The content of the urethane or urea compound can be calculated from the integral value of the hydrogen signal with dimethyl sulfoxide as an internal standard. When it was not possible to measure the content due to overlap of signals in NMR, the content was measured by the GC/MS analysis described below.

• Measuring apparatus: ECS400 from JEOL Corp.
• Measured atomic nucleus: ¹ H
• Resonance frequency: 400 MHz
• Number of scans: 256
• Measuring temperature: room temperature
• Solvent: heavy dimethylformamide hydride
• Measuring concentration: 1.5% by weight
• Chemical Shift Reference: Dimethylformamide (8.0233 ppm)

Ge/MS analysis

• GC-Apparatur: Agilent Technologies 7890A
• Einlasstemperatur: 320 °C
• Säule: DB-1 MS (30 m × 0,25 mm φ), Dicke der flüssigen Phase: 0,25 µm Säulentemperatur: 40 °C (Haltezeit: 5 Minuten), Temperaturerhöhung:
  • 20 °C/min, 320 °C (11 Minuten halten)
• MS-Apparatur: Agilent Technologies 5975C MSD
• Ionenquellentemperatur: 230 °C
• Ionisierungsverfahren: Elektronenionisierung

The dry sample is dissolved in 5 ml of methanol and analyzed. The concentration of the urethane or urea compound can be calculated as a weight percent by preparing a separate calibration curve using GC for the urethane or urea compound whose structure has been identified by NMR measurement and comparing this with the area of the urethane compound. or urea compound in the dry sample.

• GC apparatus: Agilent Technologies 7890A
• Inlet temperature: 320°C
• Column: DB-1 MS (30 m × 0.25 mm φ), liquid phase thickness: 0.25 µm Column temperature: 40 °C (holding time: 5 minutes), temperature increase:
  • 20°C/min, 320°C (hold for 11 minutes)
• MS apparatus: Agilent Technologies 5975C MSD
• Ion source temperature: 230°C
• Ionization process: electron ionization

Measuring the ratio of the maximum to minimum diameter of monofilaments

After sampling 1 m of the elastic polyurethane fiber, the diameters of all monofilaments in 5 randomly selected cross sections were measured, and the ratio of the maximum to the minimum was recorded as the ratio of the maximum to the minimum diameter of the monofilaments. The diameter of each monofilament was measured by examining a cross section of the polyurethane elastic fiber using a JSM-6510 electron microscope from JEOL Corp. observed. When the cross-sectional shape of the monofilament was a non-circular cross-section, such as an ellipse or dumbbell shape, the minimum diameter circle enclosing the entire cross-section (hereinafter also referred to as the “minimum circumference”) was drawn, and the monofilament diameter was taken as the diameter of the recorded within a minimum radius.

Measurement of the start of flow temperature of the elastic polyurethane fiber

The flow initiation temperature of the polyurethane elastic fiber is measured using a CFT-500D model flow tester (product of Shimadzu Corp.). The starting flow temperature of the elastic polyurethane fiber is measured without prior treatment to remove treating agents such as lubricants, taking a sample of 1.5 g for each measurement. The die used has a diameter of 0.5mm and a thickness of 1.0mm and a 30kg extrusion load is applied with a preheating time of 240 seconds at an initial preset temperature of 120°C and thereafter the Temperature is increased to 250 °C at a constant rate of 3 °C/min, and the stroke length (mm) and the temperature curve during this time are determined. As the temperature increases, the polymer in the toner is heated and the polymer begins to flow out of the nozzle. The temperature at this time is recorded as the flow start temperature.

Percentage elongation of the elastic polyurethane fiber on the winding body

The percentage elongation (%) of the polyurethane elastic fiber on the package was measured and calculated according to the following method.

A 0.5 m sample of the elastic polyurethane fiber was unwound from the package of the elastic polyurethane fiber in its relaxed state length (hereinafter also simply referred to as “relaxed length”), and the sample weight (g) was measured. The size of the elastic polyurethane yarn in its relaxed state (relaxed size A (dtex)) was calculated using the formula shown below. The measurement was carried out four times and the mean value was calculated. The “relaxed state” is a state of standing without load for 2 hours or more after the yarn has been unwound from the package.

relaxed size A (dtex) = sample weight (g) x 10 000/relaxed length (m)

The elastic polyurethane yarn was unwound from the bobbin of the elastic polyurethane fiber and fed through a payoff roller to a length of 50 m while maintaining the percentage elongation. The weight of the unwound yarn (g) was measured. The size of the elastic polyurethane yarn in its stretched state (print size B (dtex)) was calculated using the following formula. $$\begin{array}{l}\text{pressure size}\ddot{\text{O}}\text{ße B}\left(\text{dtex}\right)=\text{Total weight of unwound yarn}\left(\text{G}\right)\times 10000/50\\ \left(\text{m}\right)\end{array}$$

The percentage elongation (%) of the elastic polyurethane yarn on the bobbin was calculated using the following formula: $$\text{percentage elongation}\left(\%\right)=\left(\text{A}/\text{b}-1\right)\times 100$$

Monofilament separation

• 6: 0 bis 1 Trennung von 10
• 5: 2 bis 3 Trennungen von 10
• 4: 4 bis 5 Trennungen von 10
• 3: 6 bis 7 Trennungen von 10
• 2: 8 bis 9 Trennungen von 10
• 1: 10 Trennungen von 10

Using a tensile testing machine (Model RTG-1210 TENSILON from Orientech Co., Ltd.), a 50 mm long test yarn sample was pulled out under the conditions of 20 °C, 65% relative humidity at a speed of 500 mm/min until it broke, and the broken portion of the elastic fiber was observed to determine whether separation of the monofilaments had occurred. It was considered that the monofilaments had been separated if at least 1 cm of independent monofilaments were found on the torn part. The measurement was carried out 10 times for each test yarn and the number of monofilaments separated was recorded and rated using the following six-point scale:

• 6: 0 to 1 separation from 10
• 5: 2 to 3 separations out of 10
• 4: 4 to 5 separations out of 10
• 3: 6 to 7 separations out of 10
• 2: 8 to 9 separations out of 10
• 1: 10 separations of 10

Variation of running tension

• 6: Laufspannungsvariationswert < 5 (mg/dtex)
• 5: Laufspannungsvariationswert ≥ 5 (mg/dtex) und < 7 (mg/dtex)
• 4: Laufspannungsvariationswert ≥ 7 (mg/dtex) und < 10 (mg/dtex)
• 3: Laufspannungsvariationswert ≥ 10 (mg/dtex) und < 12 (mg/dtex)
• 2: Laufspannungsvariationswert ≥ 12 (mg/dtex) und < 15 (mg/dtex)
• 1: Laufspannungsvariationswert ≥ 15 (mg/dtex)

A bobbin 1, comprising 1000 m of elastic polyurethane fiber wound on a paper tube (weft spool), was placed on an apparatus as shown in 1 is shown, and conveyed at a draw ratio of 3x with an elastic fiber payout roller 2 at a speed of 10 m/min and a take-up roller 3 at a speed of 30 m/min, and the tension (mg) during the yarn running was with measured with a voltmeter 4 at intervals of 0.1 seconds over a period of 3 minutes. The standard deviation (mg) for the variation of the tension value was divided by the size of the elastic fiber, and the value was recorded as the running tension variation value (mg/dtex) and evaluated using the following six-point scale:

• 6: Running tension variation value < 5 (mg/dtex)
• 5: Running tension variation value ≥ 5 (mg/dtex) and < 7 (mg/dtex)
• 4: Running tension variation value ≥ 7 (mg/dtex) and < 10 (mg/dtex)
• 3: Running tension variation value ≥ 10 (mg/dtex) and < 12 (mg/dtex)
• 2: Running tension variation value ≥ 12 (mg/dtex) and < 15 (mg/dtex)
• 1: Running tension variation value ≥ 15 (mg/dtex)

Anti-static property while running

• 6: Absolutbetrag der während des Laufens erzeugten statischen Elektrizität < 4 (kV)
• 5: Absolutbetrag der während des Laufens erzeugten statischen Elektrizität ≥ 4 (kV) und < 4,5 (kV)
• 4: Absolutbetrag der während des Laufens erzeugten statischen Elektrizität ≥ 4,5 (kV) und < 5 (kV)
• 3: Absolutbetrag der während des Laufens erzeugten statischen Elektrizität ≥ 5 (kV) und < 5,5 (kV)
• 2: Absolutbetrag der während des Laufens erzeugten statischen Elektrizität ≥ 5,5 (kV) und < 6 (kV)
• 1: Absolutbetrag der während des Laufens erzeugten statischen Elektrizität ≥ 6 (kV)

A bobbin 1 comprising 10,000 m of elastic polyurethane fiber wound on a paper tube was placed on an apparatus as shown in 2 is shown, and conveyed in a draw ratio of 2x with an elastic fiber delivery roller 2 at a speed of 50 m / min and a take-up roller 3 at a speed of 100 m / min, and after 1 hour from the start of running, the during Static electricity generated by running on 2 mm of the yarn was measured with a digital low voltage voltmeter (product of Kasuga Denki Co., Ltd.) 5. The mean value for the static electricity values obtained was taken as static electricity generated during running (kV) and evaluated using the following six-point scale:

• 6: Absolute amount of static electricity generated during running < 4 (kV)
• 5: Absolute amount of static electricity generated during running ≥ 4 (kV) and < 4.5 (kV)
• 4: Absolute amount of static electricity generated during running ≥ 4.5 (kV) and < 5 (kV)
• 3: Absolute amount of static electricity generated during running ≥ 5 (kV) and < 5.5 (kV)
• 2: Absolute amount of static electricity generated during running ≥ 5.5 (kV) and < 6 (kV)
• 1: Absolute amount of static electricity generated during running ≥ 6 (kV)

Heat resistance of monofilaments

• 6: Zahl der Sekunden bis zum Reißen ≥ 60 Sekunden
• 5: Zahl der Sekunden bis zum Reißen ≥ 45 und < 60
• 4: Zahl der Sekunden bis zum Reißen ≥ 30 und < 45
• 3: Zahl der Sekunden bis zum Reißen ≥ 10 und < 30
• 2: Zahl der Sekunden bis zum Reißen ≥ 5 und < 10
• 1: Zahl der Sekunden bis zum Reißen < 5

A test yarn with an initial length of 7 cm was stretched by 200% (to 21 cm) and pressed against a cylindrical hot body having a cylinder with a surface temperature of 180 ° C and a diameter of 6 cm (contact part: 1 cm), and the number of seconds to rupture was measured and rated using the following six-point scale:

• 6: Number of seconds to tear ≥ 60 seconds
• 5: Number of seconds to tear ≥ 45 and < 60
• 4: Number of seconds to tear ≥ 30 and < 45
• 3: Number of seconds until tearing ≥ 10 and < 30
• 2: Number of seconds until tearing ≥ 5 and < 10
• 1: Number of seconds until tearing < 5

Resistance to yarn breakage during processing

• 6: Bewertung von 6 für alle die Eigenschaften Monofilamentauftrennung, Variation der Laufspannung, Wärmebeständigkeit der Monofilamente und antistatische Eigenschaft während des Laufens und kein Reißen des Garns während der Verarbeitu ngssch ritte
• 5: Bewertung von 5 für beliebige der Eigenschaften Monofilamentauftrennung, Variation der Laufspannung, Wärmebeständigkeit der Monofilamente und antistatische Eigenschaft während des Laufens und keine Bewertung von 4, 3, 2 oder 1. Kein Reißen des Garns während der Verarbeitungsschritte.
• 4: Bewertung von 4 für beliebige der Eigenschaften Monofilamentauftrennung, Variation der Laufspannung, Wärmebeständigkeit der Monofilamente und antistatische Eigenschaft während des Laufens und keine Bewertung von 3, 2 oder 1. Fast kein Reißen des Garns während der Verarbeitungsschritte.
• 3: Bewertung von 3 für beliebige der Eigenschaften Monofilamentauftrennung, Variation der Laufspannung, Wärmebeständigkeit der Monofilamente und antistatische Eigenschaft während des Laufens und keine Bewertung von 2 oder 1. Fast kein Reißen des Garns während der Verarbeitungsschritte.
• 2: Bewertung von 2 für beliebige der Eigenschaften Monofilamentauftrennung, Variation der Laufspannung, Wärmebeständigkeit der Monofilamente und antistatische Eigenschaft während des Laufens und keine Bewertung von 1. Nur selten Reißen des Garns während der Verarbeitungsschritte.
• 1: Bewertung von 1 für beliebige der Eigenschaften Monofilamentauftrennung, Variation der Laufspannung, Wärmebeständigkeit der Monofilamente und antistatische Eigenschaft während des Laufens mit häufigem Reißen des Garns während der Verarbeitungsschritte.

The frequency of yarn breakage when using the elastic polyurethane fiber in processing steps was evaluated using the following six-point scale:

• 6: Rating of 6 for all the properties of monofilament separation, variation of running tension, heat resistance of monofilaments and antistatic property during running and no tearing of the yarn during processing steps
• 5: Rating of 5 for any of the properties of monofilament separation, variation of running tension, heat resistance of monofilaments and antistatic property during running and no rating of 4, 3, 2 or 1. No breaking of the yarn during the processing steps.
• 4: Rating of 4 for any of the properties of monofilament separation, variation of running tension, heat resistance of monofilaments and antistatic property during running and no rating of 3, 2 or 1. Almost no breakage of the yarn during the processing steps.
• 3: Rating of 3 for any of the properties of monofilament separation, variation of running tension, heat resistance of monofilaments and antistatic property during running and no rating of 2 or 1. Almost no breakage of the yarn during the processing steps.
• 2: Rating of 2 for any of the properties of monofilament separation, variation of running tension, heat resistance of monofilaments and antistatic property during running and no rating of 1. Rarely breaking of the yarn during processing steps.
• 1: Rating of 1 for any of the properties of monofilament separation, variation of running tension, heat resistance of monofilaments and antistatic property during running with frequent yarn breakage during processing steps.

Unless otherwise specified, the polyurethane elastic fibers and packages in Examples and Comparative Examples were prepared by the following manufacturing method.

A mixture of 2000 g of polytetramethylene ether glycol with a number average molecular weight of 2000 g / mol with 400 g of 4,4'-diphenylmethane diisocyanate was reacted for 3 hours under a dry nitrogen stream at 60 ° C with stirring, giving a polyurethane prepolymer whose ends with Isocyanate groups were capped. The prepolymer was cooled to room temperature and dimethylacetamide was added until dissolved to prepare a polyurethane prepolymer solution. In addition, a solution of 33.8 g of ethylenediamine and 5.4 g of diethylamine in dry dimethylacetamide was prepared and added to the prepolymer solution at room temperature to obtain a polyurethane solution PA1 having a polyurethane solid concentration of 30% by mass and had a viscosity of 450 Pa s (30 °C). An ester or phosphoric acid ester or a tertiary amine-containing urethane or urea compound was added to PA1 and optionally mixed with it to to produce a homogeneous solution, which was then degassed under reduced pressure at room temperature and used as a spinning stock solution. The spinning stock was extruded from a spinneret having a number of holes corresponding to the desired number of filaments, and in order to adjust the ratio of the maximum to minimum diameter of the monofilaments, the temperature inside the spinning cylinder was appropriately regulated, and that Yarn was appropriately rocked during dry spinning while converging the multifilaments with a false twisting apparatus using compressed air of 0.20 MPa, and thereafter a lubricant containing an ester or phosphoric acid ester was optionally applied to the elastic polyurethane fiber, and this was wound on a paper tube to obtain a package of elastic polyurethane fiber.

Examples 1 to 8

Diethylene glycol dibenzoate (having an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.) was added to the lubricant or polymer to 200 ppm based on the total weight of the elastic polyurethane fiber and packages of the elastic polyurethane yarn for Examples 1 to 1 8 were with ratios of the maximum to minimum diameter of the monofilaments of 1.47 to 1.53 and a flow start temperature of 200 ° C or above without addition of a tertiary amine-containing urethane or urea compound, with a percentage elongation of 2% and with the Yarn size and the number of filaments changed as shown in Table 1 below. The results are shown in Table 1 below.

Examples 9 to 15

Bobbins of the elastic polyurethane yarn for Examples 9 to 15 were made with a yarn size of 620 dtex, a number of filaments of 72 and ratios of the maximum to minimum diameter of the monofilaments of 1.48 to 1.56 and a percentage elongation of 2% and below Change in the flow initiation temperatures and the contents of diethylene glycol dibenzoate (having an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.) added to the lubricant or polymer based on the total weight of the elastic polyurethane fiber as described in the Table 1 was prepared while no tertiary amine-containing urethane or urea compound was added.

It has been proven that adding an ester or phosphoric acid ester to an elastic polyurethane fiber can inhibit yarn breakage during processing. The results are shown in Table 1 below. Table 1 example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Gama size (dtex) 620 620 155 310 940 620 310 940 620 620 620 620 620 620 620 Number of filaments 72 72 18 36 72 28 36 72 72 72 72 72 72 72 72 Name of the ester or phosphoric acid ester Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Method of adding the ester or phosphoric acid ester lubricant polymer lubricant lubricant lubricant lubricant polymer polymer lubricant lubricant lubricant lubricant polymer polymer polymer Content of the ester or phosphoric acid ester 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 50ppm 100ppm 2% 5% 100ppm 2% 5% Ratio of maximum to minimum monofilament diameter 1.50 1.53 1.48 1.47 1.52 1.51 1.50 1.53 1.48 1.56 1.53 1.55 1.48 1.56 1.54 Flow start temperature (°C) 210 209 209 211 212 213 210 212 210 210 209 205 210 208 200 aromatic ring in the ester or phosphoric acid ester available available available available available available available available available available available available available available available Structure of the urethane or urea compound containing a tertiary amine 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Content of a tertiary amine-containing urethane or urea compound 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (Content of a tertiary amine-containing urethane or urea compound)/ (Content of ester or phosphoric acid ester) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 percentage elongation (%) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Gam separation 4 4 4 4 4 4 4 4 3 4 4 4 4 4 4 Variation of the running tension 6 6 6 6 6 6 6 6 6 6 6 3 6 6 3 Heat resistance of the monofilament 6 6 6 6 6 6 6 6 6 6 6 4 6 6 3 antistatic property 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Resistance to yarn breakage 3 3 3 3 3 3 3 3 3 3 3 3 3 3

Examples 16 to 21

Bobbins of the elastic polyurethane yarn for Examples 16 to 21 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of an ester or phosphoric acid ester to the lubricant in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber, ratios the maximum to minimum diameter of the monofilaments from 1.46 to 1.53, a flow start temperature of 200 ° C or above without the addition of a tertiary amine-containing urethane or urea compound, with a percentage elongation of 2% and changing the ester or phosphoric acid ester , as shown in Table 2 below. The ester or phosphoric acid ester used was methyl benzoate (having an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.), benzyl benzoate (having an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.), Trimethyl trimellitate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.), tricresyl phosphate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.), diphenyl-2-ethylhexyl phosphate ( with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.) or dibutyl phthalate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.).

It has been proven that adding an ester or phosphoric acid ester to an elastic polyurethane fiber can inhibit yarn breakage during processing. The results are shown in Table 2 below.

Examples 22 to 33 (Examples 22, 28 and 33 are not according to the invention)

Bobbins of the elastic polyurethane yarn for Examples 22 to 33 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of diethylene glycol dibenzoate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.). the lubricant or polymer in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber, with a percentage elongation of 2%, a flow start temperature of 200 ° C or above, without adding a tertiary amine-containing urethane or urea compound and with modification the ratio of the maximum to minimum diameter of the monofilaments, as shown in Table 2.

It was shown that controlling the ratio of the maximum to minimum diameter of the monofilaments can inhibit yarn breakage during processing. The results are shown in Table 2 below.

Table 2

Examples 34 and 35

Bobbins of the elastic polyurethane yarn for Examples 34 and 35 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of diethylene glycol dibenzoate (having an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.). the lubricant or polymer in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber, with ratios of the maximum to minimum diameter of the monofilaments of 1.49 to 1.52, a percentage elongation of 2%, a flow start temperature of less than 200 ° C produced without adding a urethane or urea compound containing a tertiary amine. At a flow start temperature of below 200 ° C during the production of the elastic polyurethane fibers of these examples, a polyurethane solution PU1, which was synthesized separately according to the method described below, was mixed with PA1 in a weight ratio of PA1:PU1 = 90:10 to 60:40 , and then an ester or phosphoric acid ester or a tertiary amine-containing urethane or urea compound was optionally added and mixed therewith to obtain a homogeneous solution, and then it was degassed under reduced pressure at room temperature and used as a spinning stock solution. PU1 was synthesized by reacting 2000 g of polytetramethylene ether glycol with a number average molecular weight of 2000 g/mol and 400 g of toluene diisocyanate at 60 °C for 3 hours under a dry nitrogen atmosphere with stirring to obtain a polyurethane prepolymer, the ends of which capped with isocyanate groups, and after cooling to room temperature, dimethylacetamide was added until dissolved to prepare a polyurethane prepolymer solution, while separately a solution of 110 g of 1,4-butanediol in dry dimethylacetamide was prepared at room temperature to the above prepolymer Solution was added and reacted for 3 hours with stirring at 80 ° C. It was found that controlling the flow start temperature can inhibit yarn breakage during processing. The results are shown in Table 3 below.

Examples 36 and 37

Bobbins of the elastic polyurethane yarn for Examples 36 and 37 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of an ester or phosphoric acid ester to the lubricant in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber Ratios of the maximum to minimum diameter of the monofilaments of 1.50 to 1.53, a flow start temperature of 200 ° C or above without the addition of a tertiary amine-containing urethane or urea compound, a percentage elongation of 2% and changing the ester, as it is shown in Table 3 below. The esters used were bis(2-ethylhexyl) adipate (without aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.) and trimethyl citrate (without aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.). ).

It was found that adding an ester to an elastic polyurethane fiber can inhibit yarn breakage during processing. The results are shown in Table 3 below.

Examples 38 and 39

Bobbins of the elastic polyurethane yarn for Examples 38 and 39 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of diethylene glycol dibenzoate (having an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.). the lubricant in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber, with ratios of the maximum to minimum diameter of the monofilaments of 1.48 to 1.56, a flow start temperature of 200 ° C or above without the addition of a tertiary amine containing Urethane or urea compound and changing the percentage elongation as shown in Table 3.

It was shown that controlling the percentage elongation can inhibit yarn breakage during processing. The results are shown in Table 3 below. Table 3 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Yarn size (dtex) 620 620 620 620 620 620 Number of filaments 72 72 72 72 72 72 Name of the ester or phosphoric acid ester Diethylene glycol dibenzoate Diethylene glycol dibenzoate Bis(2-ethylhexyl) adipate Trimethylcitrate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Method of adding the ester or phosphoric acid ester lubricant polymer lubricant lubricant lubricant lubricant Content of the ester or phosphoric acid ester 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm Ratio of maximum to minimum monofilament diameter 1.52 1.49 1.50 1.53 1.56 1.48 Flow start temperature (°C) 194 190 211 210 210 209 aromatic ring in the ester or phosphoric acid ester available available missing missing available available Structure of the urethane or urea compound containing a tertiary amine 0 0 0 0 0 0 Content of a tertiary amine-containing urethane or urea compound 0 0 0 0 0 0 (Content of a tertiary amine-containing urethane or urea compound)/ (Content of ester or phosphoric acid ester) 0 0 0 0 0 0 percentage elongation (%) 2 2 2 2 5 7 Yarn separation 4 4 3 3 4 4 Variation of running tension 6 6 6 6 6 4 Heat resistance of the monofilament 5 5 6 6 6 6 antistatic property 3 3 3 3 3 3 Resistance to yarn breakage 3 3 3 3 3 3

A tertiary amine-containing urethane or urea compound was synthesized according to each of the following Preparation Examples 1 to 6.

Production example 1

After 100 mmol of N-butyldiethanolamine (product of Tokyo Kasei Kogyo Co., Ltd.), 90 mmol of isophorone diisocyanate (product of Tokyo Kasei Kogyo Co., Ltd.), 100 ml of DMAc (product of Tokyo Kasei Kogyo Co., Ltd.) and 0.1 ml of dibutyltin dilaurate as a catalyst were added to a separable flask equipped with a stirrer and thermometer, the mixture was stirred at 60 °C for 2 hours to synthesize compound 4.

Production example 2

After 100 mmol of 1,1'-(N-methylimino)di-2-propanol (product of BASF Corp.), 90 mmol of dicyclohexylmethane-4,4'-diisocyanate (product of Tokyo Kasei Kogyo Co., Ltd.), 100 mL of DMAc (product of Tokyo Kasei Kogyo Co., Ltd.) and 0.1 mL of dibutyltin dilaurate as a catalyst were added to a separable flask equipped with a stirrer and thermometer, the mixture was stirred at 60 °C for 2 hours to synthesize compound 5.

Production example 3

After 100 mmol of 1,1'-{N-(t-butyl)imino}di-2-propanol (product of Tokyo Kasei Kogyo Co., Ltd.), 90 mmol of isophorone diisocyanate (product of Tokyo Kasei Kogyo Co., Ltd. ), 100 ml of DMAc (product of Tokyo Kasei Kogyo Co., Ltd.) and 0.1 ml of dibutyltin dilaurate as a catalyst were added to a separable flask equipped with a stirrer and thermometer, the mixture was kept at 60 for 2 hours °C stirred to synthesize compound 6.

Production example 4

After 60 mmol of N-(t-butyl)diethanolamine (product of Tokyo Kasei Kogyo Co., Ltd.), 40 mmol of 1,4-butanediol (product of Tokyo Kasei Kogyo Co., Ltd.), 90 mmol of dicyclohexylmethane-4, 4'-diisocyanate (product of Tokyo Kasei Kogyo Co., Ltd.), 100 ml of DMAc (product of Tokyo Kasei Kogyo Co., Ltd.) and 0.1 ml of dibutyltin dilaurate as a catalyst in a separable flask equipped with a stirrer and Thermometer equipped, the mixture was stirred at 60 °C for 2 hours to synthesize compound 7.

Production example 5

After 100 mmol of N,N-dimethylhydrazine (product of Tokyo Kasei Kogyo Co., Ltd.), 50 mmol of diphenylmethane diisocyanate (product of Tokyo Kasei Kogyo Co., Ltd.) and 100 ml of DMAc (product of Tokyo Kasei Kogyo Co., Ltd.) .) were placed in a separable flask equipped with a stirrer and thermometer, the mixture was stirred at 60 °C for 2 hours to synthesize compound 8.

Production example 6

After 100 mmol of N,N-dimethylhydrazine (product of Tokyo Kasei Kogyo Co., Ltd.), 50 mmol of hexamethylene diisocyanate (product of Tokyo Kasei Kogyo Co., Ltd.) and 100 ml of DMAc (product of Tokyo Kasei Kogyo Co., Ltd.). .) were placed in a separable flask equipped with a stirrer and thermometer, the mixture was stirred at 60 °C for 2 hours to synthesize compound 9.

Examples 40 to 45

Bobbins of the elastic polyurethane yarn for Examples 40 to 45 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of diethylene glycol dibenzoate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.). the lubricant in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber, with ratios of the maximum to minimum diameter of the monofilaments of 1.46 to 1.55, a percentage elongation of 2%, a flow start temperature of 200 ° C or above and with a tertiary amine-containing urethane or urea compound added in an amount of 2% so that the content of the tertiary amine-containing urethane or urea compound was 100 times the content of the ester or phosphoric ester. The tertiary amine-containing urethane or urea compounds used were Compounds 4 to 9 prepared in Preparation Examples 1 to 6.

It has been shown that the addition of a urethane or urea compound containing a tertiary amine can inhibit yarn breakage during processing. The results are shown in Table 4 below.

Examples 46 to 51

Bobbins of the elastic polyurethane yarn for Examples 46 to 51 were made with a yarn size of 620 dtex, a number of filaments of 72, with the addition of diethylene glycol dibenzoate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.). the lubricant in an amount of 200 ppm, based on the total weight of the elastic polyurethane fiber, with ratios of the maximum to minimum diameter of the monofilaments of 1.46 to 1.56, a percentage elongation of 2%, a flow start temperature of 200 ° C or above and changing the contents of Compound 4 prepared in Preparation Example 1 as shown in Table 4 below so that the content of the tertiary amine-containing urethane or urea compound is 0.75 to 200 times Content of the ester or phosphoric acid ester was produced.

It has been found that controlling the ratio of the content of the tertiary amine-containing urethane or urea compound to the ester content can inhibit yarn breakage during processing. The results are shown in Table 4 below.

Comparative example 1

A package of the elastic polyurethane yarn for Comparative Example 1 was made without adding an ester or phosphoric acid ester to the elastic polyurethane fiber, with a yarn size of 620 dtex, a number of filaments of 72, a ratio of the maximum to the minimum diameter of the monofilaments of 1.47, a flow start temperature of 212 ° C without adding a urethane or urea compound containing a tertiary amine and with a percentage elongation of 2%.

The yarn separated easily and suffered from frequent yarn breakage during processing. The results are shown in Table 4 below.

Comparative Examples 2 to 5

Bobbins of the elastic polyurethane yarn for Comparative Examples 2 to 5 were made with a yarn size of 620 dtex, a number of filaments of 72, with ratios of the maximum to minimum diameter of the monofilaments of 1.49 to 1.57, without the addition of a tertiary amine containing Urethane or urea compound and with a percentage elongation of 2%, while the flow initiation temperatures and the contents of diethylene glycol dibenzoate (with an aromatic ring in the compound, product of Tokyo Kasei Kogyo Co., Ltd.) added to the lubricant or polymer were changed with respect to the total weight of the polyurethane elastic fiber as shown in Table 4, and no urethane or urea compound containing a tertiary amine was added.

The yarn often broke during processing. The results are shown in Table 4 below. Table 4 Example 40 Example 41 Example 42 Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Gam size (dtex) 620 620 620 620 620 620 620 620 620 620 620 620 620 620 620 620 620 Number of filaments 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 72 Name of the ester or phosphoric acid ester Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate none Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Diethylene glycol dibenzoate Method of adding the ester or phosphoric acid ester lubricant lubricant lubricant lubricant lubricant lubricant lubricant lubricant lubricant lubricant lubricant lubricant - lubricant lubricant polymer polymer Content of the ester or phosphoric acid ester 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 200ppm 0 ppm 30 ppm 7% 30 ppm 7% Ratio of maximum to minimum monofilament diameter 1.50 1.47 1.46 1.51 1.53 1.55 1.53 1.56 1.46 1.51 1.50 1.51 1.47 1.49 1.52 1.51 1.57 Flow start temperature (°C) 210 208 211 212 209 210 209 208 211 210 212 211 212 211 200 211 195 aromatic ring in the ester or phosphoric acid ester available available available available available available available available available available available available available available available available available Structure of the urethane or urea compound containing a tertiary amine Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 Formula 9 Formula 4 Formula 4 Formula 4 Formula 4 Formula 4 Formula 4 0 0 0 0 0 Content of a tertiary amine-containing urethane or urea compound 2% 2% 2% 2% 2% 2% 150ppm 250 ppm 0.4% 1% 3% 4% 0 0 0 0 0 (Content of a tertiary amine-containing urethane or urea compound)/ (Content of ester or phosphoric acid ester) 100 100 100 100 100 100 0.75 1.25 20 50 150 200 0 0 0 0 0 percentage elongation (%) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Gam separation 6 6 6 6 6 6 4 5 6 6 6 4 1 1 4 1 4 Variation of running tension 6 6 6 6 6 6 6 6 6 6 6 6 6 6 1 6 1 Heat resistance of the monofilament 6 6 6 6 6 6 6 6 6 6 6 6 6 6 2 6 1 antistatic property 6 6 6 6 6 6 4 5 6 6 6 4 1 2 3 2 3 Resistance to yarn breakage 6 6 6 6 6 6 4 5 6 6 6 4 1 1 1 1 1

Commercial applicability

By adding a specific ester or phosphoric acid ester in a predetermined amount to the polyurethane elastic fiber of the invention, the polyurethane elastic fiber can be made resistant to separation of the monofilaments, has a small variation in running tension and is resistant to breakage of the monofilaments by heat, whereby the tearing of the yarn during processing is sufficiently inhibited. The elastic polyurethane fiber of the invention can therefore be suitably used in the manufacture of underwear, stockings, compression garments and diapers.

List of reference symbols

1

Bobbin of elastic fiber

2

drain roller

3

Recording roll

4

Tension meter

5

digital low voltage voltmeter

Claims (14)

An elastic polyurethane fiber in the form of a multifilament yarn, wherein the elastic polyurethane fiber comprises an ester or phosphoric acid ester which is the product of condensation of a compound A and a compound B in a content of 50 ppm to 5% based on the weight of the elastic polyurethane fiber, wherein Compound A is selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms, tricarboxylic acids with 4 to 30 carbon atoms and phosphoric acid and compound B from monools with 1 to 30 carbon atoms, diols with a molecular weight of 3000 g / mol or less and Triols having a molecular weight of 3000 g/mol or less are selected, and wherein the ratio of the maximum to the minimum diameter of monofilaments constituting the multifilament yarn made of elastic polyurethane fibers is 1.1 to 2.0. Elastic polyurethane fiber according to Claim 1 , wherein the start of flow temperature of the elastic polyurethane fiber measured with a flow tester is 200 ° C or more. Elastic polyurethane fiber according to one of Claims 1 or 2 , wherein the content of ester or phosphoric ester is 50 ppm or more and 1.5% or less based on the weight of the elastic polyurethane fiber. Elastic polyurethane fiber according to one of Claims 1 until 3 , wherein compound A is selected from monocarboxylic acids with 4 to 30 carbon atoms, dicarboxylic acids with 4 to 30 carbon atoms and tricarboxylic acids with 4 to 30 carbon atoms. Elastic polyurethane fiber according to one of Claims 1 until 4 , wherein compound A is selected from dicarboxylic acids having 4 to 30 carbon atoms and tricarboxylic acids having 4 to 30 carbon atoms or compound B is selected from diols having a molecular weight of 3000 g/mol or less and triols having a molecular weight of 3000 g/mol or less. Elastic polyurethane fiber according to one of Claims 1 until 5 , wherein the ester or phosphoric ester which is the product of the condensation of a compound A and a compound B has an aromatic ring. Elastic polyurethane fiber according to one of Claims 1 until 6 which further comprises a tertiary amine-containing urethane or urea compound in a proportion of 0.01% or more and 5% or less. Elastic polyurethane fiber according to Claim 7 , wherein the tertiary amine-containing urethane compound is a urethane compound having a repeating unit represented by the following formula (1):

where R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, R ₂ and R ₃ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. Elastic polyurethane fiber according to Claim 7 , wherein the tertiary amine-containing urethane compound is a urethane compound having: a repeating unit represented by the following formula (1):

wherein R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, R ₂ and R ₃ are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms; and a repeating unit represented by formula (2):

where R ₅ is a divalent hydrocarbon group having 5 to 30 carbon atoms and R ₆ is a divalent hydrocarbon group or polyoxyalkylene group having 1 to 10 carbon atoms. Elastic polyurethane fiber according to Claim 7 , wherein the tertiary amine-containing urea compound is a urea compound represented by the following formula (3):

where R ₇ and R ₈ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and R ₉ is a divalent hydrocarbon group having 5 to 30 carbon atoms. Elastic polyurethane fiber according to one of Claims 7 until 10 , wherein the content of the tertiary amine-containing urethane or urea compound is greater than the content of the ester or phosphoric ester which is the product of the condensation of a compound A and a compound B. Elastic polyurethane fiber according to Claim 11 , wherein the content of the tertiary amine-containing urethane or urea compound is 20 times to 150 times the content of the ester or phosphoric acid ester which is the product of the condensation of a compound A and a compound B. Winding body of an elastic polyurethane fiber according to one of Claims 1 until 12 . Winding body according to Claim 13 , wherein the percentage elongation of the elastic polyurethane fiber on the bobbin is 5% or less.

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